53892-48-1

Upstream product

• 186581-53-3 diazomethane 
• 110-44-1 hexa-2,4-dienoic acid 
• 108965-77-1 (E)-(2S,3S)-2-Hydroxy-3-trimethylsilanyl-hex-4-enoic acid methyl ester 
• 127379-37-7 Methyl (trans,Z)-3-(2-Methyl-5,8-dioxaspiro<3.4>oct-1-yl)-2-propenoate 

Downstream Products

• 5837-72-9 methyl (E)-4-oxo-2-butenoate 
• 142334-76-7 methyl (2Z,4E)-6-oxohexa-2,4-dienolate 

Relevant academic research and scientific papers

Vinylcyclobutane-Cyclohexane Rearrangements: Zwitterions as Discrete Intermediates

Donor-acceptor-substituted vinylcyclobutanes 1 rearrange to cyclohexenes 2 at temperatures between 20 and 195 deg C.In solvents of low polarity, cycloreversion competes with ring enlargement.Under acidic conditions, addition of nucleophiles to vinylcyclobutanes 1 with ring opening is observed.Stereospecificity of rearrangement and cycloreversion are functions of temperature, solvent polarity and acid catalysis.Strong dependence on solvent polarity is found for the rates of both reactions.The mechanisms of the thermally induced and acid-catalyzed reactions are discussed on the basis of stereospecificity, kinetic parameters and trapping of intermediates.Two structurally different zwitterions 13 and 14 are proposed as intermediates, one of which is responsible for rearrangement, the other for diastereomerization and cycloreversion.

Stereoselective Synthesis of (2E,4E)- and (2Z,4E)-2,4-Alkadienoates by the Ester Enolate Claisen Rearrangement of (E)-1-Alkyl-3-trimethylsilyl-2-propenyl Glycolates Followed by the Peterson Reaction

The ester enolate Claisen rearrangement of (E)-1-alkyl-3-trimethylsilyl-2-propenyl glycolates gave (E)-erythro-2-hydroxy-3-trimethylsilyl-4-alkenoates with high diastereoselectivity, which were stereoselectively converted into (2E,4E)- and (2Z,4E)-2,4-alkadienoates by the Peterson reaction.